CN110283264A - A kind of bipyridyl iron complex and the preparation method and application thereof - Google Patents
A kind of bipyridyl iron complex and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110283264A CN110283264A CN201910570841.9A CN201910570841A CN110283264A CN 110283264 A CN110283264 A CN 110283264A CN 201910570841 A CN201910570841 A CN 201910570841A CN 110283264 A CN110283264 A CN 110283264A
- Authority
- CN
- China
- Prior art keywords
- iron complex
- bipyridyl
- reaction
- bipyridyl iron
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 bipyridyl iron complex Chemical class 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 143
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000009826 distribution Methods 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 18
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003426 co-catalyst Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 125000001539 acetonyl group Chemical group [H]C([H])([H])C(=O)C([H])([H])* 0.000 claims 1
- 230000003712 anti-aging effect Effects 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 38
- 229920000642 polymer Polymers 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 46
- 235000019441 ethanol Nutrition 0.000 description 46
- 239000012300 argon atmosphere Substances 0.000 description 22
- 229920001971 elastomer Polymers 0.000 description 21
- 238000005406 washing Methods 0.000 description 21
- 239000000806 elastomer Substances 0.000 description 17
- 238000010791 quenching Methods 0.000 description 15
- 230000000171 quenching effect Effects 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 150000001638 boron Chemical class 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241001443715 Fusarium oxysporum f. sp. conglutinans Species 0.000 description 1
- 239000005065 High vinyl polybutadiene Substances 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/01—High molecular weight, e.g. >800,000 Da.
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A kind of bipyridyl iron complex and the preparation method and application thereof, belongs to isoprene hydrocarbon catalytic polymerization field.It is at high cost for catalyst used in current polyisoprene synthesis process, the technical problem of microstructure controllable adjustment ability difference, the present invention provides a kind of bipyridyl iron complexes, it is reacted and is prepared with the ethanol solution of ferrous salt or molysite by the ethanol solution of bipyridyl, the bipyridyl iron complex is used as major catalyst in polyprene polymerization, shows as high activity, and obtained polymer molecular weight is high, molecular weight distribution is relatively narrow, and the present invention can be used for the industrialized production of polyisoprene.
Description
Technical field
The present invention relates to isoprene catalytic polymerization fields, and in particular to a kind of bipyridyl iron complex and preparation method thereof
With application.
Background technique
For a long time, the rolling resistance of tyre stock and anti-slippery this hamper " green tire " development always to contradiction
It promotes, anti-form-1,4- polyisoprene rubber (TPI), high vinyl polybutadiene rubber (HVBR) and 3,4- polyisoprene
The appearance of the new materials such as rubber (3,4-PIP) opened up a new way for the research application of " green tire ".3,4- polyisoprene
(3,4-PIP) there is high wet-sliding resistant performance, low rolling resistance and good damping performance, can be used for manufacturing high-performance wheel
Tire；The water resistance and air-tightness of this isoprene rubber are close to butyl rubber；It also can be with EP rubbers and with preparing high service performance
Vulcanizate, meet manufacture vehicle section bar technique requirement.For a long time, it is poly- to be widely used in 3,4- for different metal catalyst
In isoprene research.AlEt3–Ti(OR)4(R=alkyl group) system, (dmpe)2CrCl2- MAO system constantly quilt
It designs and is applied in isoprene polymerization, and obtain the polyisoprene of higher 3,4- selectivity.Wang Fosong seminar is for the first time
The crystallization of high 3,4- selectivity is obtained with a small amount of nitrogenous electron reagent three compositions system of praseodynium iron-triisobutyl aluminium-
Polyisoprene.So far, there are still many problems in industrialized production for 3,4- polyisoprene rubber: 1) iron is catalyzed
High 3,4- selectivity polyisoprene reactivity is not high, and system reactive species structure can not determine that catalytic mechanism is indefinite.2) dilute
Although earth metal is catalyzed, 3,4- is selectively excellent, catalyst is at high cost, 3) microstructure of titanium system catalytic polymer can control
Energy saving power is poor.
Summary of the invention
At high cost for catalyst used in current polyisoprene synthesis process, microstructure controllable adjustment ability is poor
The technical issues of, the present invention provides a kind of bipyridyl iron complex, structural formulas are as follows:
Wherein X are as follows: any one of chlorine, bromine or levulinic ketone group；N=2 or 3.
It further limits, the bipyridyl iron complex, structural formula is one of following structural formula:
It further limits, above-mentioned 3rd bipyridyl iron complex is the acetylacetone,2,4-pentanedione of a molecule pyridine and a molecule
The complex compound that ferrous iron is formed.
The present invention also provides the preparation methods of above-mentioned bipyridyl iron complex, under atmosphere of inert gases, by bipyridyl
Ethanol solution mixed with the ethanol solution of ferrous salt or molysite according to 1:1 molar equivalent ratio, after reaction filtering, filtrate successively
It is concentrated, be dried to obtain bipyridyl iron complex.
The present invention also provides application of the above-mentioned bipyridyl iron complex in isoprene polymerization, refer in anhydrous and oxygen-free
Under the conditions of, under atmosphere of inert gases, carried out after bipyridyl iron complex, isoprene monomer, co-catalyst and solvent mixing
Polymerization reaction, is added quencher after reaction, and separating-purifying obtains polyisoprene product；The temperature of the polymerization reaction
It is -40 DEG C~50 DEG C, 25 DEG C of preferable reaction temperature；Polymerization time is 1min -240min；Preferred polymeric time 10min；It is described to help
Catalyst is methylaluminoxane (MAO) or alkyl aluminum, and the general structure of the methylaluminoxane is [- Al (CH3) O-] n, wherein n
For the natural number of 4-40；The alkyl aluminum is trimethyl aluminium, triethyl aluminum or triisobutyl aluminium.
It further limits, the solvent is the mixed of one of toluene, petroleum ether, pentane or hexane or two kinds or more
It closes, the concentration of isoprene monomer in a solvent is 2-10mol/L；The preferred toluene of solvent, and make isoprene monomer
Concentration in toluene is 4mol/L.
It further limits, the quencher is methanolic HCl solution, and wherein the volume ratio of methanol and hydrochloric acid is 50:1；With
Amount is 2 times of the solvent volume.
It further limits, age resister can also be added after reaction, the age resister is mass percent
For the ethanol solution of 1%2,6- di-tert-butyl-4-methy phenol, dosage is the 20% of the solvent volume.
Further limit, in reaction system, the molar ratio of ferro element in isoprene monomer and bipyridyl iron complex
For (1000-20000): 1；Preferred molar ratio is 2000:1；The mole of bipyridyl iron complex ferro element is 1-10 μm of ol；It is excellent
Selecting molar ratio is 2000:1；The molar ratio of the ferro element in aluminium element and bipyridyl iron complex in co-catalyst is (1-
1000):1。
It further limits, further includes dealkylating reagent in the reaction system, the dealkylating reagent is B
(C6F5)3, [Ph3C][B(C6F5)4] or [PhNMe2H][B(C6F5)4] one kind；Preferably [Ph3C][B(C6F5)4]；De- alkyl
Changing boron element and ferro element molar ratio in bipyridyl iron complex in reagent is (1-10): 1；Preferred molar ratio 1:1.
It further limits, polyisoprene number-average molecular weight obtained above is 50,000-50 ten thousand, and molecular weight distribution is
1.2-4.0；Cis--Isosorbide-5-Nitrae structure proportion range is 20%-50%, and anti-form-1,4 structure proportion ranges are 0%-
20%, 3,4 structure proportion ranges are 50%-80%.
In above-mentioned polymerization reaction, influence of the charging sequence to reactivity and selectivity is little.Charging sequence can be with are as follows:
(1) co-catalyst, solvent after isoprene sequentially adds, add major catalyst and carry out polymerization reaction to obtain
To polyisoprene；
Or (2) co-catalyst, solvent, after major catalyst sequentially adds, add isoprene carry out polymerization reaction from
And obtain polyisoprene；
Or (3) major catalyst, toluene, after isoprene sequentially adds, add co-catalyst carry out polymerization reaction from
And obtain polyisoprene.
Beneficial effect
The present invention is using cheap iron as metal center, using bipyridyl as main skeleton, provides a kind of new and effective iron catalysis
Agent system.Isoamyl two is catalyzed as major catalyst, methylaluminoxane (MAO) as co-catalyst using bipyridyl ferrous metal complex
The polymerization of alkene, bipyridyl iron complex catalyst system provided by the invention have molecular structure clear, high activity and excellent
Selectivity (3,4- selectivity a maximum of about of 80%), and obtained opposite high molecule mass (number-average molecular weight is 50,000-50 ten thousand),
The polymer of narrower molecular weight distribution (PDI=1.2-4.0).Acquired technical effect is summarized as follows:
1, the iron catalyst system of the application is the specific bipyridyl iron complex of molecular structure, is mainly used for being catalyzed isoamyl two
Alkene polymerization, play a role as major catalyst, bipyridyl iron complex prepare it is simple and easy to get, it is at low cost；In isoprene polymerization
In show as high activity, obtained polymer molecular weight is high, and molecular weight distribution is relatively narrow, and the microstructure of polymer can pass through tune
Major catalyst structure is saved to regulate and control, meanwhile, the activity of reaction depends on the major catalyst of different substituents and variety classes are helped and urged
Agent.
2, isoprene polymerization reaction can both carry out in two components of methylaluminoxane, in alkyl aluminum and can also go
It is carried out in three components of alkylating reagent composition.
3, polyisoprene number-average molecular weight of the present invention is 50,000-50 ten thousand, molecular weight distribution 1.2-4.0；It is suitable
Formula-Isosorbide-5-Nitrae structure proportion range is 20%-50%, and anti-form-1,4 structure proportion ranges are 0%-20%, 3,4 structures
Proportion range is 50%-80%.
Detailed description of the invention
The crystalline structure schematic diagram of Fig. 1 bipyridyl iron complex 3.
Specific embodiment
The present invention will be further described combined with specific embodiments below, but the present invention should not be limited by the examples.
The synthesis of 1. bipyridyl iron complex 1 of embodiment.
Bipyridyl iron complex described in the present embodiment, structural formula are as follows:
It is prepared via a method which to obtain:
Under argon atmosphere, anhydrous FeCl is added into the Schlenk bottle of 50mL2(164.8mg, 1.3mmol), at 60 DEG C
It is dissolved with 10mL dehydrated alcohol；Ethyl alcohol (10mL) solution of 2,2 '-bipyridyls (203.0mg, 1.3mmol) is added dropwise to system again
In.It is reacted 1 hour at 60 DEG C.Chinese red complex is precipitated from system, filtering, and with cold ethanol washing 2 times, concentration removes molten
Agent is dried in vacuo 12h, obtains Chinese red solid product 1, yield 74%.
Mass spectral analysis: C10H8Cl2FeN2: [M-Cl]+: theoretical value: 246.9720；Measured value: 246.9718.
Elemental analysis: C10H8Cl2FeN2: theoretical value: C, 42.45%；H, 2.85%；N, 9.90%；Measured value: C,
42.72%；H, 2.67%；N, 9.82%.
Embodiment 2: the synthesis of bipyridyl iron complex 2.
Bipyridyl iron complex described in the present embodiment, structural formula are as follows:
It is prepared via a method which to obtain:
Under argon atmosphere, anhydrous FeCl is added into the Schlenk bottle of 50mL3(210.6mg, 1.3mmol), at 60 DEG C
It is dissolved with 10mL dehydrated alcohol；By 2,2, ' ethyl alcohol (10mL) solution of-bipyridyl (203.0mg, 1.3mmol) is added dropwise to system again
In.It is reacted 1 hour at 60 DEG C.Yellow complex is precipitated from system, filtering, and with cold ethanol washing 2 times, concentration removes molten
Agent is dried in vacuo 12h, obtains apricot solid product 2, yield 77%.
Mass spectral analysis: C10H8Cl3FeN2: [M-Cl]+: theoretical value: 281.9408；Measured value: 281.9404.
Elemental analysis: C10H8Cl3FeN2: theoretical value: C, 37.73%；H, 2.53%；N, 8.80%；Measured value: C,
37.98%；H, 2.26%；N, 8.55%.
Embodiment 3: the synthesis of bipyridyl iron complex 3.
Bipyridyl iron complex described in the present embodiment, structural formula are as follows:
It is prepared via a method which to obtain:
Under argon atmosphere, anhydrous Fe (acac) is added into the Schlenk bottle of 50mL2(127.0mg, 0.5mmol), in 60
It is dissolved at DEG C with 6mL dehydrated alcohol；Ethyl alcohol (4mL) solution of 2,2 '-bipyridyls (78.1mg, 0.5mmol) is added dropwise to body again
In system.Half an hour is reacted at 60 DEG C, is then restored to being stirred overnight at room temperature.Filtrate is collected by filtration, is concentrated, with cold ethanol washing
2 times, it is dried in vacuo 12h, obtains yellow-brown solid product 3, yield 68%.
Mass spectral analysis: C20H22FeN2O4: [M+H]+: theoretical value: 411.1002；Measured value: 410.0998.
Elemental analysis: C20H22FeN2O4: theoretical value: C, 58.55%；H, 5.41%；N, 6.83%；Measured value: C,
58.34%；H, 5.53%；N, 7.09%.
The crystal structure that bipyridyl iron complex 3 is also further analyzed in the present embodiment is as shown in Figure 1.
Embodiment 4: the synthesis of bipyridyl iron complex 4.
Bipyridyl iron complex described in the present embodiment, structural formula are as follows:
It is prepared via a method which to obtain:
Under argon atmosphere, anhydrous Fe (acac) is added into the Schlenk bottle of 50mL3(211.9mg, 0.6mmol), in 60
It is dissolved at DEG C with 6mL dehydrated alcohol；Ethyl alcohol (4mL) solution of 2,2 '-bipyridyls (93.7mg, 0.6mmol) is added dropwise to body again
In system.Half an hour is reacted at 60 DEG C, is then restored to being stirred overnight at room temperature.Filtrate is collected by filtration, is concentrated, with cold ethanol washing
2 times, it is dried in vacuo 12h, obtains red brown solid product 4, yield 68%.
Mass spectral analysis: C25H29FeN2O6: [M+H]+: theoretical value: 510.1448；Measured value: 510.1443.
Elemental analysis: C25H29FeN2O6: theoretical value: C, 58.95%；H, 5.74%；N, 5.50%；Measured value: C,
58.54%；H, 5.61%；N, 5.85%.
Application of the above-mentioned bipyridyl iron complex in isoprene polymerization.In polymerization reaction catalyst system, the research point
For two component catalyst systems (being added without dealkylating reagent) and three-component catalyze system (dealkylating reagent is added), below will
In conjunction with specific implementation case, the present invention will be further described.
Isoprene polymerization reaction: in catalytic polymerization, bipyridyl iron complex, can be independent as major catalyst
It is added, can also be added in the form of its dichloromethane solution.
Embodiment 5-7 is to verify the molar ratio of co-catalyst and major catalyst to isoprene polymerization activity and selectivity shadow
It rings.
Embodiment 5. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, anhydrous and oxygen-free toluene 5mL are added MAO (5mmol, 500eq.),
Isoprene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution (MeOH/HCl=of 10mL at 25 DEG C
50/1) quenching reaction, and the ethanol solution 1mL that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added, then
Twice with ethanol washing, elastomer polymer is obtained.Yield: > 99%, number-average molecular weight (Mn): 24.5 ten thousand, molecular weight distribution
(PDI): 1.8.Different structure proportion: cis-1,4- structure account for 27%, trans-1, and 4- structure accounts for 9%, and 3,4- structures account for
64%.
Embodiment 6. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, anhydrous and oxygen-free toluene 5mL, addition MAO (10mmol,
1000eq.), isoprene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution of 10mL at 25 DEG C
(MeOH/HCl=50/1) quenching reaction, and it is molten that the ethyl alcohol that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added
Then twice with ethanol washing liquid 1mL obtains elastomer polymer.Yield: > 99%, number-average molecular weight (Mn): 16.6 ten thousand, point
Son amount distribution (PDI): 2.5.Different structure proportion: cis-1,4- structure account for 31%, trans-1, and 4- structure accounts for 0%, 3,
4- structure accounts for 69%.
Embodiment 7. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, anhydrous and oxygen-free toluene 5mL, addition MAO (2.5mmol,
250eq.), isoprene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution of 10mL at 25 DEG C
(MeOH/HCl=50/1) quenching reaction, and it is molten that the ethyl alcohol that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added
Then twice with ethanol washing liquid 1mL obtains elastomer polymer.Yield: > 99%, number-average molecular weight (Mn): 26.5 ten thousand, point
Son amount distribution (PDI): 2.0.Different structure proportion: cis-1,4- structure account for 22%, trans-1, and 4- structure accounts for 6%, 3,
4- structure accounts for 72%.
Embodiment 8-9 is that verifying solvent influences isoprene polymerization activity and selectivity.
Embodiment 8. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, anhydrous and oxygen-free petroleum ether 5mL, addition MAO (5mmol,
500eq.), isoprene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution of 10mL at 25 DEG C
(MeOH/HCl=50/1) quenching reaction and be added mass percent be 1%2,6- di-tert-butyl-4-methy phenol ethyl alcohol it is molten
Then twice with ethanol washing liquid 1mL obtains elastomeric polymer.Yield: > 99%, number-average molecular weight (Mn): 44.5 ten thousand, molecule
Amount distribution (PDI): 2.1.Different structure proportion: cis-1,4- structure account for 23%, trans-1, and 4- structure accounts for 8%, 3,4-
Structure accounts for 69%.
Embodiment 9. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, anhydrous and oxygen-free hexane 5mL are added MAO (5mmol, 500eq.),
Isoprene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution (MeOH/HCl=of 10mL at 25 DEG C
50/1) quenching reaction, and the ethanol solution 1mL that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added, then
Twice with ethanol washing, elastomer polymer is obtained.Yield: > 99%, number-average molecular weight (Mn): 38.3 ten thousand, molecular weight distribution
(PDI): 2.1.Different structure proportion: cis-1,4- structure account for 26%, trans-1, and 4- structure accounts for 4%, and 3, -4 structures account for
70%.
Embodiment 10-12 is that verifying temperature influences isoprene polymerization activity and selectivity.
Embodiment 10. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, anhydrous and oxygen-free toluene 5mL are added MAO (5mmol, 500eq.),
Isoprene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution (MeOH/HCl=of 10mL at 50 DEG C
50/1) quenching reaction, and the ethanol solution 1mL that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added, then
Twice with ethanol washing, elastomer polymer is obtained.Yield: > 99%, number-average molecular weight (Mn): 18.9 ten thousand, molecular weight distribution
(PDI): 3.8.Different structure proportion: cis-1,4- structure account for 21%, trans-1, and 4- structure accounts for 11%, and 3,4- structures account for
68%.
Embodiment 11. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, dry toluene 5mL are added MAO (5mmol, 500eq.), isoamyl
Diene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution (MeOH/HCl=50/1) of 10mL at 0 DEG C
Quenching reaction, and the ethanol solution 1mL that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added, then use ethyl alcohol
It washes twice, obtains elastomer polymer.Yield: > 99%, number-average molecular weight (Mn): 35.4 ten thousand, molecular weight distribution (PDI):
1.4.Different structure proportion: cis-1,4- structure account for 30%, trans-1, and 4- structure accounts for 0%, and 3,4- structures account for 70%.
Embodiment 12. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, anhydrous and oxygen-free toluene 5mL are added MAO (5mmol, 500eq.),
Isoprene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution (MeOH/HCl=of 10mL at -25 DEG C
50/1) quenching reaction, and the ethanol solution 1mL that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added, then
Twice with ethanol washing, elastomer polymer is obtained.Yield: 58%, number-average molecular weight (Mn): 36.8 ten thousand, molecular weight distribution
(PDI): 1.5.Different structure proportion: cis-1,4- structure account for 30%, trans-1, and 4- structure accounts for 0%, and 3,4- structures account for
70%.
Embodiment 13-14 is that verifying amount of monomer influences isoprene polymerization activity and selectivity.
Embodiment 13. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, dry toluene 25mL are added MAO (5mmol, 500eq.), different
Pentadiene (10mL, 100.0mmol) polymerize 10min, the reaction methanolic HCl solution (MeOH/HCl=of 10mL at 25 DEG C
50/1) quenching reaction, and the ethanol solution 1mL that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added, then
Twice with ethanol washing, elastomer polymer is obtained.Yield: > 99%, number-average molecular weight (Mn): 44.5 ten thousand, molecular weight distribution
(PDI): 2.0.Different structure proportion: cis-1,4- structure account for 26%, trans-1, and 4- structure accounts for 5%, and 3,4- structures account for
69%.
Embodiment 14. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, anhydrous and oxygen-free toluene 50mL, addition MAO (5mmol,
500eq.), isoprene (20mL, 200.0mmol) polymerize 10min, the reaction methanolic HCl solution of 10mL at 25 DEG C
(volume ratio=50/1 MeOH/HCl) quenching reaction, and it is 1%2,6- di-tert-butyl-4-methy phenol that mass percent, which is added,
Then twice with ethanol washing ethanol solution 1mL obtains elastomer polymer.Yield: 65%, number-average molecular weight (Mn): 54.3
Ten thousand, molecular weight distribution (PDI): 2.2.Different structure proportion: cis-1,4- structure account for 28%, trans-1, and 4- structure accounts for
2%, 3,4- structures account for 70%.
Embodiment 15-17 is that verifying catalyst type influences isoprene polymerization activity and selectivity.
Embodiment 15. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 2 and be prepared into
The catalyst bipyridyl iron complex (3.2mg, 10 μm of ol) arrived, anhydrous and oxygen-free toluene 5mL are added MAO (5mmol, 500eq.),
Isoprene (2mL, 20.0mmol) polymerize 10min, reaction methanolic HCl solution (the MeOH/HCl body of 10mL at 25 DEG C
Product ratio=50/1) quenching reaction, and the ethanol solution that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added
Then twice with ethanol washing 1mL obtains elastomer polymer.Yield: > 99%；Number-average molecular weight (Mn): 20.1 ten thousand, molecule
Amount distribution (PDI): 2.3；Different structure proportion: cis-1,4- structure account for 28%, trans-1, and 4- structure accounts for 0%, 3,4-
Structure accounts for 72%.
Embodiment 16. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 3 and be prepared into
The catalyst bipyridyl iron complex (4.1mg, 10 μm of ol) arrived, anhydrous and oxygen-free toluene 5mL, methylaluminoxane (5mmol,
500eq.), isoprene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution of 10mL at 25 DEG C
(volume ratio=50/1 MeOH/HCl) quenching reaction, and it is 1%2,6- di-tert-butyl-4-methy phenol that mass percent, which is added,
Then twice with ethanol washing ethanol solution 1mL obtains elastomer polymer.Yield: > 99%, number-average molecular weight (Mn):
16.6 ten thousand, molecular weight distribution (PDI): 2.5.Different structure proportion: cis-1,4- structure account for 31%, trans-1,4- structure
0% is accounted for, 3,4 structures account for 69%.
Embodiment 17. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 4 and be prepared into
The catalyst bipyridyl iron complex (5.1mg, 10 μm of ol) arrived, anhydrous and oxygen-free toluene 5mL, methylaluminoxane (5mmol,
500eq.), isoprene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution of 10mL at 25 DEG C
(volume ratio=50/1 MeOH/HCl) quenching reaction, and it is 1%2,6- di-tert-butyl-4-methy phenol that mass percent, which is added,
Then twice with ethanol washing ethanol solution 1mL obtains elastomer polymer.Yield: > 99%, number-average molecular weight (Mn):
15.9 ten thousand, molecular weight distribution (PDI): 2.3.Different structure proportion: cis-1,4- structure account for 31%, trans-1,4- structure
0% is accounted for, 3,4 structures account for 69%.
Embodiment 18-21 is the case where verifying catalyst contains dealkylating reagent under the conditions of three components, i.e., in system
Under, the influence to isoprene polymerization activity and selectivity.
Embodiment 18. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds anhydrous and oxygen-free toluene
5mL, trimethyl aluminium (200 μm of ol), the 2mL bis- of catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) prepared by embodiment 1
Chloromethanes solution stirs 2min, and boron salt [Ph is added3C][B(C6F5)4] (10 μm of ol), stirring 2min, isoprene (2mL,
20mmol), 10min is polymerize at 25 DEG C, reaction is quenched with the methanolic HCl solution (volume ratio=50/1 MeOH/HCl) of 10mL
Reaction, and the ethanol solution 1mL that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added, then use ethanol washing
Twice, elastomer polymer is obtained.Yield: > 99%, number-average molecular weight (Mn): 5.8 ten thousand, molecular weight distribution (PDI): 3.1.No
With structure proportion: cis-1,4- structure account for 45%, trans-1, and 4- structure accounts for 0%, and 3,4 structures account for 55%.
Embodiment 19. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds dry toluene 5mL,
Triethyl aluminum (200 μm of ol), the 2mL dichloro of catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) prepared by embodiment 1First Alkane solution stirs 2min, and boron salt [Ph is added3C][B(C6F5)4] (10 μm of ol), stirring 2min, isoprene (2mL, 20Mmol), 10min is polymerize at 25 DEG C, reaction is quenched with the methanolic HCl solution (volume ratio=50/1 MeOH/HCl) of 10mL
Reaction, and the ethanol solution 1mL that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added, then use ethanol washing
Twice, elastomer polymer is obtained.Yield: > 99%, number-average molecular weight (Mn): 5.7 ten thousand, molecular weight distribution (PDI): 2.9.No
With structure proportion: cis-1,4- structure account for 38%, trans-1, and 4- structure accounts for 2%, and 3,4- structures account for 60%.
Embodiment 20. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds anhydrous and oxygen-free toluene
5mL, triisobutyl aluminium (200 μm of ol), the 2mL of catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) prepared by embodiment 1
Dichloromethane solution stirs 2min, and boron salt [Ph is added3C][B(C6F5)4] (10 μm of ol), stirring 2min, isoprene (2mL,
20mmol), 10min is polymerize at 25 DEG C, reaction is quenched with the methanolic HCl solution (volume ratio=50/1 MeOH/HCl) of 10mL
Reaction, and the ethanol solution 1mL that mass percent is 1%2,6- di-tert-butyl-4-methy phenol is added, then use ethanol washing
Twice, elastomer polymer is obtained.Yield: > 99%, number-average molecular weight (Mn): 5.8 ten thousand, molecular weight distribution (PDI): 3.0.No
With structure proportion: cis-1,4- structure account for 32%, trans-1, and 4- structure accounts for 0%, and 3,4- structures account for 68%.
Embodiment 21. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds anhydrous and oxygen-free toluene
5mL, MAO (200 μm of ol), the 2mL methylene chloride of catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) prepared by embodiment 1
Solution stirs 2min, and boron salt [Ph is added3C][B(C6F5)4] (10 μm of ol), stirring 2min, isoprene (2mL, 20mmol),
It polymerize 10min, reaction methanolic HCl solution (volume ratio=50/1 MeOH/HCl) quenching reaction of 10mL at 25 DEG C, and adds
Enter the ethanol solution 1mL that mass percent is 1%2,6- di-tert-butyl-4-methy phenol then twice with ethanol washing to obtain
Elastomer polymer.Yield: > 99%, number-average molecular weight (Mn): 6.5 ten thousand, molecular weight distribution (PDI): 2.7.Shared by different structure
Ratio: cis-1,4- structure account for 25%, trans-1, and 4- structure accounts for 14%, and 3,4- structures account for 61%.
Embodiment 22. wishes in Lake (Schlenk) pipe in 25mL under argon atmosphere, sequentially adds embodiment 1 and be prepared into
The catalyst bipyridyl iron complex (2.8mg, 10 μm of ol) arrived, anhydrous and oxygen-free toluene 5mL are added MAO (5mmol, 500eq.),
Isoprene (2mL, 20.0mmol) polymerize 10min, the reaction methanolic HCl solution (MeOH/HCl=of 10mL at 25 DEG C
50/1) then twice with ethanol washing quenching reaction obtains elastomer polymer.Yield: > 99%, number-average molecular weight (Mn):
24.5 ten thousand, molecular weight distribution (PDI): 1.8.Different structure proportion: cis-1,4- structure account for 27%, trans-1,4- structure
9% is accounted for, 3,4- structures account for 64%.
Above-described embodiment is preferable case study on implementation of the invention, but case study on implementation of the invention is not by enumerating embodiment
Limitation, other any changes made without departing from core of the invention thought with principle, modification, combine, substitution, simplify be accordingly to be regarded as
Equivalent substitution should be all included within protection scope of the present invention.
Claims (10)
1. a kind of bipyridyl iron complex, which is characterized in that structural formula are as follows:Wherein X are as follows: chlorine, bromine or acetyl
Any one of acetonyl；N=2 or 3.
2. bipyridyl iron complex according to claim 1, which is characterized in that its structural formula is one in following structural formula
Kind:
3. the preparation method of bipyridyl iron complex of any of claims 1 or 2, which is characterized in that under atmosphere of inert gases,
The ethanol solution of bipyridyl is mixed with the ethanol solution of ferrous salt or molysite according to a mole 1:1 molar equivalent ratio, after reaction
Filtering, filtrate is successively concentrated, is dried to obtain bipyridyl iron complex.
4. application of the bipyridyl iron complex of any of claims 1 or 2 in isoprene polymerization, which is characterized in that in nothing
Under water oxygen free condition, under atmosphere of inert gases, bipyridyl iron complex, isoprene monomer, co-catalyst and solvent mixing
After carry out polymerization reaction, quencher is added after reaction, separating-purifying obtains polyisoprene product；The polymerization reaction
Temperature is -40 DEG C~50 DEG C, and polymerization time is 1min -240min；The co-catalyst be methylaluminoxane MAO or alkyl aluminum,
The general structure of the methylaluminoxane is [- Al (CH3) O-] n, wherein n is the natural number of 4-40；The alkyl aluminum is front three
Base aluminium, triethyl aluminum or triisobutyl aluminium.
5. application according to claim 4, which is characterized in that the solvent is in toluene, petroleum ether, pentane or hexane
One or two or more kinds of mixtures, the concentration of isoprene monomer in a solvent are 2-10mol/L.
6. application according to claim 4, which is characterized in that the quencher be methanolic HCl solution, wherein methanol with
The volume ratio of hydrochloric acid is 50:1；Dosage is 2 times of the solvent volume.
7. application according to claim 4, which is characterized in that it is additionally added age resister after reaction, it is described anti-aging
Agent is the ethanol solution that mass percent is 1%2,6- di-tert-butyl-4-methy phenol, and dosage is the solvent volume
20%.
8. application according to claim 4, which is characterized in that in reaction system, isoprene monomer is matched with bipyridyl iron
The molar ratio for closing ferro element in object is (1000-20000): 1；The mole of ferro element is 1-10 μ in bipyridyl iron complex
mol；The molar ratio of ferro element is (1-1000) in aluminium element and bipyridyl iron complex in co-catalyst: 1.
9. application according to claim 4, which is characterized in that it further include dealkylating reagent in the reaction system, institute
Stating dealkylating reagent is B (C6F5)3, [Ph3C][B(C6F5)4] or [PhNMe2H][B(C6F5)4] one kind；Dealkylating reagent
Ferro element molar ratio is (1-10) in middle boron element and bipyridyl iron complex: 1.
10. application according to claim 4, which is characterized in that obtained polyisoprene number-average molecular weight is 50,000-50
Ten thousand, molecular weight distribution 1.2-4.0；Cis--Isosorbide-5-Nitrae structure proportion range is 20%-50%, anti-form-1,4 structure institute accountings
Example range is 0%-20%, and 3,4 structure proportion ranges are 50%-80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910570841.9A CN110283264A (en) | 2019-06-27 | 2019-06-27 | A kind of bipyridyl iron complex and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910570841.9A CN110283264A (en) | 2019-06-27 | 2019-06-27 | A kind of bipyridyl iron complex and the preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110283264A true CN110283264A (en) | 2019-09-27 |
Family
ID=68019356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910570841.9A Pending CN110283264A (en) | 2019-06-27 | 2019-06-27 | A kind of bipyridyl iron complex and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110283264A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112266432A (en) * | 2020-10-27 | 2021-01-26 | 中国科学院青岛生物能源与过程研究所 | Efficient preparation method of high molecular weight polylaurene with high 3, 4-structure content |
| WO2021042258A1 (en) * | 2019-09-03 | 2021-03-11 | 中国科学院青岛生物能源与过程研究所 | Bipyridine iron complex, preparation method thereof and application in polymerization of conjugated diene |
| CN112521538A (en) * | 2020-11-24 | 2021-03-19 | 中国科学院青岛生物能源与过程研究所 | Efficient preparation method and application of ultra-high molecular weight beta-farnesene |
| CN112694136A (en) * | 2021-02-07 | 2021-04-23 | 杭州金丰环保科技有限公司 | Synthetic method of polymeric ferric sulfate and polymeric ferric sulfate |
| CN114249849A (en) * | 2021-09-28 | 2022-03-29 | 中国科学院青岛生物能源与过程研究所 | High-branched-chain iron-based conjugated diene polymer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018220538A1 (en) * | 2017-05-31 | 2018-12-06 | Versalis S.P.A. | Butadiene-isoprene diblock copolymers and process for the preparation thereof |
-
2019
- 2019-06-27 CN CN201910570841.9A patent/CN110283264A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018220538A1 (en) * | 2017-05-31 | 2018-12-06 | Versalis S.P.A. | Butadiene-isoprene diblock copolymers and process for the preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| GIOVANNI RICCI ET AL.: ""Polymerization of 1,3-dienes with iron complexes based catalysts Influence of the ligand on catalyst activity and stereospecificity"", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021042258A1 (en) * | 2019-09-03 | 2021-03-11 | 中国科学院青岛生物能源与过程研究所 | Bipyridine iron complex, preparation method thereof and application in polymerization of conjugated diene |
| CN112266432A (en) * | 2020-10-27 | 2021-01-26 | 中国科学院青岛生物能源与过程研究所 | Efficient preparation method of high molecular weight polylaurene with high 3, 4-structure content |
| CN112521538A (en) * | 2020-11-24 | 2021-03-19 | 中国科学院青岛生物能源与过程研究所 | Efficient preparation method and application of ultra-high molecular weight beta-farnesene |
| CN112694136A (en) * | 2021-02-07 | 2021-04-23 | 杭州金丰环保科技有限公司 | Synthetic method of polymeric ferric sulfate and polymeric ferric sulfate |
| CN114249849A (en) * | 2021-09-28 | 2022-03-29 | 中国科学院青岛生物能源与过程研究所 | High-branched-chain iron-based conjugated diene polymer and preparation method thereof |
| CN114249849B (en) * | 2021-09-28 | 2023-11-03 | 中国科学院青岛生物能源与过程研究所 | Highly branched iron conjugated diene polymer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110283264A (en) | A kind of bipyridyl iron complex and the preparation method and application thereof | |
| CN110452272B (en) | Bipyridine iron complex, preparation method thereof and application thereof in conjugated diene polymerization | |
| CN106632764B (en) | A kind of Fe-series catalyst and preparation method thereof and the application in isoprene polymerization | |
| CN108530571B (en) | Iron-based alkylpyridinylimine catalyst and preparation method and application thereof | |
| CN110305169B (en) | Substituted bipyridyl ferric iron complex and preparation method and application thereof | |
| EP3808753B1 (en) | Bipyridine iron complex, preparation method thereof and application in polymerization of conjugated diene | |
| CN109053937B (en) | Alkyl substituted pyridylamine iron-based catalyst and preparation method and application thereof | |
| CN108586641B (en) | High-efficiency iron-based catalyst for catalyzing isoprene polymerization and preparation method and application thereof | |
| CN109912732B (en) | Bond-forming pyridylamine iron-based catalyst and preparation method and application thereof | |
| CN109851700A (en) | A kind of trident pyridinimine Fe-series catalyst and the preparation method and application thereof | |
| CN114249849B (en) | Highly branched iron conjugated diene polymer and preparation method thereof | |
| CN109134730B (en) | Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof | |
| CN111303214B (en) | Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same | |
| CN108659055B (en) | Iron complex based on flexible framework, preparation method thereof and application thereof in isoprene polymerization | |
| CN108641026B (en) | Application of benzyl imine pyridine iron complex in preparation of isoprene rubber | |
| CN110305168A (en) | A kind of substitution bipyridyl ferrous coordination compound and the preparation method and application thereof | |
| CN111233938B (en) | Pyrimidineacetylacetone ferrous complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same | |
| CN108659036B (en) | Vanadium complex, preparation method thereof and application thereof in isoprene polymerization | |
| CN112707937B (en) | Heteroaromatic ring tridentate pyridine imine iron complex, preparation method thereof and application thereof in catalysis of polymerization of conjugated diene | |
| Wang et al. | Methylene bridged binuclear bis (imino) pyridyl iron (II) complexes and their use as catalysts together with Al (i-Bu) 3 for ethylene polymerization | |
| CN114736245B (en) | Pyridine-2-oxime-iron complex, preparation method thereof and application thereof in preparation of conjugated diene rubber | |
| WO2022183467A1 (en) | Heteroaromatic ring tridentate pyridine imine iron complex, preparation method therefor, and application thereof in catalysis of conjugated diene polymerization | |
| CN115873045B (en) | N, N-bidentate iron carboxylate complex, preparation method and application thereof in conjugated diene polymerization | |
| CN113583058B (en) | Iron complex and preparation method thereof, iron catalyst and application thereof, and polybutadiene and preparation method thereof | |
| CN118546280A (en) | Process for preparing a poly-conjugated diene, products and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190927 |
|
| RJ01 | Rejection of invention patent application after publication |